EP1748972A2 - Dosable pyrotechnic composition usable in the form of a thermal fuse for a gas generator and a gas generator comprising a compound containing said composition - Google Patents

Dosable pyrotechnic composition usable in the form of a thermal fuse for a gas generator and a gas generator comprising a compound containing said composition

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Publication number
EP1748972A2
EP1748972A2 EP05770900A EP05770900A EP1748972A2 EP 1748972 A2 EP1748972 A2 EP 1748972A2 EP 05770900 A EP05770900 A EP 05770900A EP 05770900 A EP05770900 A EP 05770900A EP 1748972 A2 EP1748972 A2 EP 1748972A2
Authority
EP
European Patent Office
Prior art keywords
composition
composition according
pyrotechnic
binder
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05770900A
Other languages
German (de)
French (fr)
Other versions
EP1748972B1 (en
Inventor
Frédéric MARLIN
Gérard MARINO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ArianeGroup SAS
Original Assignee
SNPE Materiaux Energetiques SA
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Publication date
Application filed by SNPE Materiaux Energetiques SA filed Critical SNPE Materiaux Energetiques SA
Publication of EP1748972A2 publication Critical patent/EP1748972A2/en
Application granted granted Critical
Publication of EP1748972B1 publication Critical patent/EP1748972B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones
    • C06B45/14—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones a layer or zone containing an inorganic explosive or an inorganic explosive or an inorganic thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
    • B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
    • B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
    • B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
    • B60R21/264—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic
    • B60R21/2644—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic using only solid reacting substances, e.g. pellets, powder

Definitions

  • the dosable pyrotechnic composition usable as a thermal fuse in an ⁇ az generator and ⁇ az generator including a compound before said composition The present invention relates to the pyrotechnic generation of gas. It relates more particularly to auto-ignition compositions, the role of which is to trigger a gas generator preventively when the latter is subjected to an abnormally high temperature.
  • a gas generator makes it possible, thanks to the initiation of a pyrotechnic charge generating gas known as the main charge, to generate in a very short time a quantity of gas for example to inflate a protective cushion.
  • a pyrotechnic composition playing the role of thermal fuse allows the main gas generating charge to be ignited before this charge reaches its temperature of Ignition.
  • composition playing the role of thermal fuse must have a self-ignition temperature significantly lower than that of the gas-generating composition
  • the composition must be placed in a reproducible manner in a preferred heat transfer zone so that the self-ignition takes place in a reproducible manner before the operation of the gas-generating composition; -
  • the composition must have, for a low mass (generally less than 200 mg), a reaction enthalpy sufficiently high to allow its initiation while limiting its impact on the normal operation of the generator.
  • the composition must be able to pass all the mechanical and thermal qualification tests of the generator and must disturb the normal operation of the generator as little as possible, for example in terms of ballistics or the toxicity of the gases generated.
  • Most of the formulations used as thermal fuses meet the first and third criteria presented above.
  • composition used as a thermal fuse comprising a compound such as a metal oxide and a compound chosen from oxalates, peroxodisulfates, permanganates, nitrates, sulfamates ...
  • composition may include an explosive such as oxynitrotriazolone (ONTA) or guanidine nitrate.
  • the composition described in this document can be mixed with the main pyrotechnic charge of the gas generator, optionally using a bonding agent.
  • the composition may represent from 0.1 to 20% and preferably from 0.1 to 5% of the total mass of the main pyrotechnic charge of the generator.
  • composition used as a thermal fuse can be separated from the main pyrotechnic charge.
  • the composition must be placed in a particularly thermally exposed zone in order to be able to be initiated before the main pyrotechnic charge in the event of abnormal heating of the generator.
  • the composition can then take the form of pellets.
  • the aforementioned patent stresses that the composition, for example in the form of pellets, must be placed in a thermally exposed zone.
  • he does not mention any means of integrating the pellets. This is important, because it can have a notable influence on the functioning of the generator in self-ignition as well as on its cost price. With a composition in the form of pellets, it is indeed difficult to obtain reproducibility in the operation of the thermal fuse composition.
  • US Patent 5,834,679 describes formulations used as a thermal fuse:
  • a handling aid a solvent, aqueous or organic.
  • Said solvent makes removal possible but considerably increases the processing of said removal (which must in particular include the elimination of said solvent: the drying of the deposited product).
  • an aqueous solvent is likely to cause corrosion problems (hence the intervention provided, in said US patent, for a protective layer), an organic solvent involves the delicate management of volatile organic compounds (VOCs) ...
  • the aim of the invention is therefore to propose a pyrotechnic composition intended to be used as a thermal fuse in a gas generator, which can be easily integrated into said pyrotechnic gas generator and which allows perfect reproducibility during self-ignition operation of the generator.
  • compositions of a pyrotechnic compound suitable as a thermal fuse in a gas generator comprising a pyrotechnic charge, said pyrotechnic compound having a self-ignition temperature lower than that of the pyrotechnic charge of the generator so as to be able to initiate combustion the pyrotechnic charge, in the event of abnormal heating of the generator, before said pyrotechnic charge reaches its self-ignition temperature, said composition being characterized in that it comprises a binder, said binder being chosen from the family of epoxides or in that of polybutadienes, said binder being present in the composition at a determined rate so that said composition can be dosed and deposited in the form of an adhesive on any suitable support of the generator.
  • the pyrotechnic composition per se (without addition of solvent) is dosable and depositable like an adhesive, which allows it to be easily placed in the gas generator without using specific means of integration.
  • the composition according to the invention can be deposited, for example using a dispenser, in the form of an adhesive, to the desired mass and to the desired location in the generator, and this ensuring good thermal contact with the support on which it is deposited. Good thermal contact as well as the possibility of sticking the composition on a heat conducting metal part of the generator makes it possible to improve the functioning of the generator in self-ignition compared to generators using existing solutions.
  • the composition according to the invention differs from the conventional formulations used in automotive safety in terms of its functional characteristics.
  • the composition according to the invention must not meet certain criteria specific to the conventional compositions used in motor vehicle safety. These criteria are, for example, the search for a particular burning rate or the need to obtain low-toxic gases.
  • the composition according to the invention must simply: - resist the thermal and mechanical stresses exerted on the generator, - be compatible with the pyrotechnic charges generating gas present in the generator, - have the lowest possible self-ignition temperature.
  • the invention is therefore a question of obtaining a product which is completely stable at 110 ° C. and which reacts quickly and exothermically above a temperature T greater than 110 ° C. and closest to 110 ° C. (between 155 ° C and 185 ° C for most of the products tested according to the invention).
  • the temperature of 110 ° C. corresponds to a temperature of a stability test commonly carried out for the formulations used in automotive safety.
  • the pyrotechnic composition of the invention is characterized by the nature of the binder it contains and by the rate of said binder therein.
  • Said binder is chosen from the family of epoxies or from that of polybutadienes (crosslinkable, thermosetting binders); it is present at a rate such that the composition can be dosed and deposited in the form of an adhesive (without the intervention of a solvent). It intervenes in a quantity such that it ensures the function of glue.
  • said binder within the compositions, performs the three functions: - cohesion of charges,
  • said binder is generally present at a rate of at least
  • the level of binder varies according to the exact nature of the binder.
  • the main criteria for choosing the binder are the feasibility of mixing at the target charge rate, compatibility with the charges at a temperature of 110 ° C. and obtaining a lively combustion for a low mass allowing the initiation of the composition. gas generator. After having been deposited on its support, the composition hardens by crosslinking.
  • the binder serves as a deposition vector and participates in the combustion of the composition as a reducing agent.
  • the binder has no influence on obtaining a low self-ignition temperature.
  • the low self-ignition temperature is obtained thanks to the charges which are introduced into the binder.
  • the composition comprises an oxidizing / reducing mixture.
  • an oxidizing / reducing mixture must make it possible to obtain the correct self-ignition temperature.
  • the binder is an epoxy binder
  • the oxidant chosen is an alkali metal chlorate
  • the reducing agent is a sugar.
  • the sufficient self-ignition temperature is obtained thanks to the alkali metal chlorate / sugar couple.
  • the binder for example an epoxy resin, is present at a mass percentage of between 18 and 22% of the total mass of the composition.
  • the alkali metal chlorate is sodium or potassium chlorate and it is present at a mass percentage of between 30 and 50% of the total mass of the composition.
  • the sugar is present at a mass percentage of between 15 and 25% of the total mass of the composition.
  • the composition comprises aluminum and an alkali metal perchlorate, to improve combustion and increase the calorimetric potential.
  • the aluminum is present at a mass percentage of between 5 and 15% of the total mass of the composition.
  • the alkali metal perchlorate is potassium perchlorate, this compound being present in a proportion of less than 20% of the total mass of the composition.
  • the composition comprises an oxidizing compound and a catalyst for the decomposition of this oxidizing compound.
  • the binder is an epoxy resin, the oxidizer of ammonium perchlorate and the decomposition catalyst a ferrocene compound.
  • the epoxy resin is present at a mass percentage of between 15 and 30%, advantageously between 16 and 25%, of the total mass of the composition.
  • the ammonium perchlorate is present at a mass percentage of between 60 to 88%, advantageously between 68 and 88%, of the total mass of the composition.
  • Another object of the invention is to provide a gas generator in which a compound acting as a thermal fuse can be easily integrated in a particularly thermally exposed area.
  • a pyrotechnic gas generator comprising a main pyrotechnic charge generating gas making it possible, for example, to inflate a protective cushion, this generator being characterized in that it comprises a self-igniting pyrotechnic compound having a composition as defined in one of the embodiments above, and the self-ignition temperature of which is lower than that of the main pyrotechnic charge.
  • the mixture of various particle sizes of ammonium perchlorate as well as the level of binder allows the rheology of the paste obtained during the mixing of the raw materials to be adapted to the requirements for depositing and preserving the product during the implementation period.
  • the main average characteristics as thermal fuse of the formulations according to Example 1 are as follows: - Auto-ignition temperature by progressive heating at a speed of 5 ° C / min. between 180 and 190 ° C. - DSC decomposition peak at 5 ° C / min, peak onset around 180 ° C. - Thermal stability acquired during vacuum stability test at 110 ° C. - Operation retained after passage 400 h at 107 ° C.
  • the self-ignition temperature is obtained by lowering the decomposition temperature of ammonium perchlorate using decomposition catalysts.
  • the epoxy binder acts as a reducing agent during combustion.
  • the average characteristics as thermal fuse of the formulations according to Example 2 are the following: Self-ignition temperature by progressive heating at a speed of 5 ° C / min. between 178 and 185 ° C. - DSC decomposition peak at 5 ° C / min, peak onset around 180 ° C. - Thermal stability acquired during vacuum stability test at 110 ° C. - Operation retained after passage 400 h at 107 ° C.
  • Example 2 the autoinflammation temperature is obtained using the chlorate / sugar couple which, in the absence of a binder, allows autoinflammation to be obtained around 160 ° C.
  • Sodium chlorate can be replaced by potassium chlorate.
  • Coating the chlorate in a binder makes it possible to obtain a product compatible with oxidants based on ammonium ions (such as, for example, ammonium perchlorate).
  • the DSC test (for "Differential Scanning Calorimetry") used in examples 1 to 2 above is a thermal analysis method which makes it possible to measure the thermal power released or absorbed by a product as a function of a rise program. temperature (within examples 1 to 2, rise of 5 ° C per minute). This method makes it possible to measure, for example, specific heats, reaction enthalpies or phase change energies.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

The invention relates to a pyrotechnic compound composition usable in the form of a thermal fuse for a gas generator comprising a pyrotechnic charge, wherein the autoignition temperature of said pyrotechnic compound is lower than the autoignition temperature of the pyrotechnic charge of the generator in such a way that it initiates the combustion of the pyrotechnic charge before that the temperature thereof attains the autoignition point in the case of abnormal heating. The inventive composition is characterised in that it is dosable in the form of glue and applicable through the entire suitable support of the generator.

Description

Composition pyrotechnique dosable utilisable comme fusible thermique dans un générateur de αaz et générateur de αaz incluant un composé avant ladite composition La présente invention concerne la génération pyrotechnique de gaz. Elle concerne plus particulièrement les compositions d'autoinflammation dont le rôle est de déclencher préventivement un générateur de gaz lorsque celui-ci est soumis à une température anormalement élevée. Un générateur de gaz permet, grâce à l'initiation d'une charge pyrotechnique génératrice de gaz dite charge principale, de générer en un temps très court une quantité de gaz par exemple pour gonfler un coussin de protection. Lors d'une brusque montée en température, causée par exemple par un incendie, la charge pyrotechnique du générateur ne va pas brûler normalement et peut réagir de manière violente et même exploser, exposant les personnes environnantes à des graves dangers. Afin de prévenir cette initiation intempestive et incontrôlée du générateur de gaz provoquée par un échauffement anormal, une composition pyrotechnique jouant le rôle de fusible thermique permet la mise à feu de la charge génératrice de gaz principale avant que cette charge n'atteigne sa température d'autoinflammation. Pour que la composition utilisée remplisse parfaitement sa fonction de fusible thermique, plusieurs critères doivent être respectés. D'une manière générale, ces critères sont les suivants :The dosable pyrotechnic composition usable as a thermal fuse in an αaz generator and αaz generator including a compound before said composition The present invention relates to the pyrotechnic generation of gas. It relates more particularly to auto-ignition compositions, the role of which is to trigger a gas generator preventively when the latter is subjected to an abnormally high temperature. A gas generator makes it possible, thanks to the initiation of a pyrotechnic charge generating gas known as the main charge, to generate in a very short time a quantity of gas for example to inflate a protective cushion. During a sudden rise in temperature, caused for example by a fire, the pyrotechnic charge of the generator will not burn normally and may react violently and even explode, exposing the surrounding persons to serious dangers. In order to prevent this untimely and uncontrolled initiation of the gas generator caused by abnormal heating, a pyrotechnic composition playing the role of thermal fuse allows the main gas generating charge to be ignited before this charge reaches its temperature of Ignition. For the composition used to fulfill its function as a thermal fuse perfectly, several criteria must be met. In general, these criteria are as follows:
- la composition jouant le rôle de fusible thermique doit disposer d'une température d'autoinflammation significativement inférieure à celle de la composition génératrice de gaz ;the composition playing the role of thermal fuse must have a self-ignition temperature significantly lower than that of the gas-generating composition;
- la composition doit être disposée de manière reproductible dans une zone de transfert thermique privilégiée pour que l'autoinflammation ait lieu de manière reproductible avant le fonctionnement de la composition génératrice de gaz ; - la composition doit présenter, pour une masse faible (généralement inférieure à 200 mg), une enthalpie de réaction suffisamment élevée pour permettre son initiation tout en limitant son impact sur le fonctionnement normal du générateur. En plus de ces caractéristiques, la composition doit pouvoir passer toutes les épreuves de qualification mécaniques et thermiques du générateur et doit perturber le moins possible le fonctionnement normal du générateur, par exemple au niveau de la balistique ou de la toxicité des gaz générés. La plupart des formulations utilisées comme fusible thermique répondent bien aux premier et troisième critères présentés ci-dessus. C'est le cas dans le brevet US 6,453,816 qui décrit une composition pyrotechnique utilisée comme fusible thermique comprenant un composé tel qu'un oxyde métallique et un composé choisi parmi les oxalates, les peroxodisulfates, les permanganates, les nitrates, sulfamates... La composition peut comprendre un explosif tel que l'oxynitrotriazolone (ONTA) ou le nitrate de guanidine. La composition décrite dans ce document peut être mélangée à la charge pyrotechnique principale du générateur de gaz, en utilisant éventuellement un agent de liaison. Dans ce cas, la composition peut représenter de 0,1 à 20% et préférentiel lement de 0,1 à 5% de la masse totale de la charge pyrotechnique principale du générateur. Ce brevet prévoit également que la composition utilisée comme fusible thermique peut être séparée de la charge pyrotechnique principale. Dans ce cas, la composition doit être disposée dans une zone particulièrement exposée thermiquement pour pouvoir être initiée avant la charge pyrotechnique principale en cas d'échauffement anormal du générateur. La composition peut alors prendre la forme de pastilles. Le brevet précité souligne que la composition, par exemple sous forme de pastilles, doit être placée dans une zone exposée thermiquement. Cependant, il ne mentionne aucun moyen d'intégration des pastilles. Ceci a son importance, car cela peut avoir une influence notable sur le fonctionnement du générateur en autoinflammation ainsi que sur son prix de revient. Avec une composition sous forme de pastilles, il est en effet difficile d'obtenir une reproductibilité dans le fonctionnement de la composition fusible thermique. Le brevet US 5,834,679 décrit des formulations utilisées comme fusible thermique :the composition must be placed in a reproducible manner in a preferred heat transfer zone so that the self-ignition takes place in a reproducible manner before the operation of the gas-generating composition; - The composition must have, for a low mass (generally less than 200 mg), a reaction enthalpy sufficiently high to allow its initiation while limiting its impact on the normal operation of the generator. In addition to these characteristics, the composition must be able to pass all the mechanical and thermal qualification tests of the generator and must disturb the normal operation of the generator as little as possible, for example in terms of ballistics or the toxicity of the gases generated. Most of the formulations used as thermal fuses meet the first and third criteria presented above. This is the case in US Patent 6,453,816 which describes a pyrotechnic composition used as a thermal fuse comprising a compound such as a metal oxide and a compound chosen from oxalates, peroxodisulfates, permanganates, nitrates, sulfamates ... composition may include an explosive such as oxynitrotriazolone (ONTA) or guanidine nitrate. The composition described in this document can be mixed with the main pyrotechnic charge of the gas generator, optionally using a bonding agent. In this case, the composition may represent from 0.1 to 20% and preferably from 0.1 to 5% of the total mass of the main pyrotechnic charge of the generator. This patent also provides that the composition used as a thermal fuse can be separated from the main pyrotechnic charge. In this case, the composition must be placed in a particularly thermally exposed zone in order to be able to be initiated before the main pyrotechnic charge in the event of abnormal heating of the generator. The composition can then take the form of pellets. The aforementioned patent stresses that the composition, for example in the form of pellets, must be placed in a thermally exposed zone. However, he does not mention any means of integrating the pellets. This is important, because it can have a notable influence on the functioning of the generator in self-ignition as well as on its cost price. With a composition in the form of pellets, it is indeed difficult to obtain reproducibility in the operation of the thermal fuse composition. US Patent 5,834,679 describes formulations used as a thermal fuse:
- dosables et déposables du fait de l'intervention, en leur sein, d'un auxiliaire de manipulation : un solvant, aqueux ou organique. Ledit solvant rend possible la dépose mais alourdit considérablement la mise en oeuvre de ladite dépose (qui doit notamment inclure l'élimination dudit solvant : le séchage du produit déposé). Par ailleurs, un solvant aqueux est susceptible d'engendrer des problèmes de corrosion (d'où l'intervention prévue, dans ledit brevet US, d'une couche protectrice), un solvant organique implique la gestion délicate de composés organiques volatils (COV) ...- dosable and depositable due to the intervention, within them, of a handling aid: a solvent, aqueous or organic. Said solvent makes removal possible but considerably increases the processing of said removal (which must in particular include the elimination of said solvent: the drying of the deposited product). Furthermore, an aqueous solvent is likely to cause corrosion problems (hence the intervention provided, in said US patent, for a protective layer), an organic solvent involves the delicate management of volatile organic compounds (VOCs) ...
- à faible taux de liant (ledit liant représente au plus 5% en poids de la composition et ne peut, à un tel taux, assurer un collage efficace) ... Le but de l'invention est donc de proposer une composition pyrotechnique destinée à être utilisée comme fusible thermique dans un générateur de gaz, qui peut être facilement intégrée dans ledit générateur pyrotechnique de gaz et qui permette une parfaite reproductibilité lors du fonctionnement en autoinflammation du générateur. Ce but est atteint par une composition d'un composé pyrotechnique convenant comme fusible thermique dans un générateur de gaz comprenant une charge pyrotechnique, ledit composé pyrotechnique ayant une température d'autoinflammation inférieure à celle de la charge pyrotechnique du générateur de manière à pouvoir initier en combustion la charge pyrotechnique, en cas d'échauffement anormal du générateur, avant que ladite charge pyrotechnique n'atteigne sa température d'autoinflammation, ladite composition étant caractérisée en ce qu'elle comporte un liant, ledit liant étant choisi dans la famille des époxydes ou dans celle des polybutadiènes, ledit liant étant présent dans la composition à un taux déterminé de sorte que ladite composition puisse être dosée et déposée sous la forme d'une colle sur tout support approprié du générateur. Selon l'invention, la composition pyrotechnique per se (sans ajout de solvant) est dosable et déposable comme une colle, ce qui lui permet de pouvoir être disposée facilement dans le générateur de gaz sans avoir recours à des moyens spécifiques d'intégration. La composition selon l'invention peut être déposée, par exemple à l'aide d'un doseur, sous la forme d'une colle, à la masse souhaitée et à l'emplacement désiré dans le générateur et ceci en assurant un bon contact thermique avec le support sur lequel elle est déposée. Le bon contact thermique ainsi que la possibilité de coller la composition sur une partie métallique conductrice de chaleur du générateur permet d'améliorer le fonctionnement du générateur en autoinflammation par rapport aux générateurs utilisant des solutions existantes. La solution de l'invention permet d'obtenir un bon fonctionnement même dans le cas où le composé obtenu aurait une température d'autoinflammation élevée, supérieure aux températures d'autoinflammation de pastilles ou de poudres. Selon l'invention, la composition selon l'invention se démarque des formulations classiques utilisées en sécurité automobile au niveau de ses caractéristiques fonctionnelles. En effet, la composition selon l'invention ne doit pas répondre à certains critères spécifiques aux compositions classiques utilisées en sécurité automobile. Ces critères sont par exemple la recherche d'une vitesse de combustion particulière ou la nécessité d'obtenir des gaz peu toxiques. La composition selon l'invention doit simplement : - résister aux contraintes thermiques et mécaniques exercées sur le générateur, - être compatibles avec les charges pyrotechniques génératrices de gaz présentes dans le générateur, - avoir une température d'autoinflammation la plus basse possible. Selon l'invention, il s'agit donc d'obtenir un produit totalement stable à 110°C et qui réagisse rapidement et de manière exothermique au-delà d'une température T supérieure à 110°C et la plus proche de 110°C (entre 155°C et 185°C pour la plupart des produits testés selon l'invention). La température de 110°C correspond à une température d'un test de stabilité couramment effectué pour les formulations utilisées en sécurité automobile. La composition pyrotechnique de l'invention se caractérise par la nature du liant qu'elle renferme et par le taux dudit liant en son sein. Ledit liant est choisi dans la famille des époxydes ou dans celle des polybutadienes (liants reticulables, thermodurcissables) ; il est présent à un taux tel que la composition peut être dosée et déposée sous la forme d'une colle (sans intervention de solvant). Il intervient en une quantité telle qu'il assure la fonction de colle. En fait, ledit liant, au sein des compositions, assure les trois fonctions : - de cohésion des charges,- Low rate of binder (said binder represents at most 5% by weight of the composition and cannot, at such a rate, ensure effective bonding) ... The aim of the invention is therefore to propose a pyrotechnic composition intended to be used as a thermal fuse in a gas generator, which can be easily integrated into said pyrotechnic gas generator and which allows perfect reproducibility during self-ignition operation of the generator. This object is achieved by a composition of a pyrotechnic compound suitable as a thermal fuse in a gas generator comprising a pyrotechnic charge, said pyrotechnic compound having a self-ignition temperature lower than that of the pyrotechnic charge of the generator so as to be able to initiate combustion the pyrotechnic charge, in the event of abnormal heating of the generator, before said pyrotechnic charge reaches its self-ignition temperature, said composition being characterized in that it comprises a binder, said binder being chosen from the family of epoxides or in that of polybutadienes, said binder being present in the composition at a determined rate so that said composition can be dosed and deposited in the form of an adhesive on any suitable support of the generator. According to the invention, the pyrotechnic composition per se (without addition of solvent) is dosable and depositable like an adhesive, which allows it to be easily placed in the gas generator without using specific means of integration. The composition according to the invention can be deposited, for example using a dispenser, in the form of an adhesive, to the desired mass and to the desired location in the generator, and this ensuring good thermal contact with the support on which it is deposited. Good thermal contact as well as the possibility of sticking the composition on a heat conducting metal part of the generator makes it possible to improve the functioning of the generator in self-ignition compared to generators using existing solutions. The solution of the invention makes it possible to obtain good operation even in the case where the compound obtained has a high auto-ignition temperature, higher than the auto-ignition temperatures of pellets or powders. According to the invention, the composition according to the invention differs from the conventional formulations used in automotive safety in terms of its functional characteristics. In fact, the composition according to the invention must not meet certain criteria specific to the conventional compositions used in motor vehicle safety. These criteria are, for example, the search for a particular burning rate or the need to obtain low-toxic gases. The composition according to the invention must simply: - resist the thermal and mechanical stresses exerted on the generator, - be compatible with the pyrotechnic charges generating gas present in the generator, - have the lowest possible self-ignition temperature. According to the invention, it is therefore a question of obtaining a product which is completely stable at 110 ° C. and which reacts quickly and exothermically above a temperature T greater than 110 ° C. and closest to 110 ° C. (between 155 ° C and 185 ° C for most of the products tested according to the invention). The temperature of 110 ° C. corresponds to a temperature of a stability test commonly carried out for the formulations used in automotive safety. The pyrotechnic composition of the invention is characterized by the nature of the binder it contains and by the rate of said binder therein. Said binder is chosen from the family of epoxies or from that of polybutadienes (crosslinkable, thermosetting binders); it is present at a rate such that the composition can be dosed and deposited in the form of an adhesive (without the intervention of a solvent). It intervenes in a quantity such that it ensures the function of glue. In fact, said binder, within the compositions, performs the three functions: - cohesion of charges,
- de participation active à la réaction pyrotechnique, et- active participation in the pyrotechnic reaction, and
- de colle sur le support (directement sur le support. Il n'y a a priori nul besoin de prévoir une couche protectrice et/ou d'accrochage). A cette fin, ledit liant est généralement présent à raison d'au moins- glue on the support (directly on the support. There is a priori no need to provide a protective and / or bonding layer). To this end, said binder is generally present at a rate of at least
15% en masse de la masse totale de la composition. Il est avantageusement présent à raison de moins de 30% en masse, très avantageusement présent à raison de moins de 25% en masse, de la masse totale de la composition. Il intervient, en tout état de cause, à un taux raisonnable, compatible avec les caractéristiques de combustion recherchées pour ladite composition. Le taux de liant varie suivant la nature exacte du liant. Les critères principaux de choix du liant sont la faisabilité du mélange au taux de charge objectif, la compatibilité avec les charges à une température de 110°C et l'obtention d'une combustion vive pour une masse faible permettant l'initiation de la composition génératrice de gaz. Après avoir été déposée sur son support la composition durcit par réticulation. Selon l'invention, dans la composition, le liant sert de vecteur de dépose et participe à la combustion de la composition en tant que réducteur. Cependant, il n'a aucune influence sur l'obtention d'une température d'autoinflammation basse. La température d'autoinflammation basse est obtenue grâce aux charges qui sont introduites dans le liant.15% by mass of the total mass of the composition. It is advantageously present in an amount of less than 30% by mass, very advantageously present in an amount of less than 25% by mass, of the total mass of the composition. It intervenes, in any event, at a reasonable rate, compatible with the combustion characteristics sought for said composition. The level of binder varies according to the exact nature of the binder. The main criteria for choosing the binder are the feasibility of mixing at the target charge rate, compatibility with the charges at a temperature of 110 ° C. and obtaining a lively combustion for a low mass allowing the initiation of the composition. gas generator. After having been deposited on its support, the composition hardens by crosslinking. According to the invention, in the composition, the binder serves as a deposition vector and participates in the combustion of the composition as a reducing agent. However, it has no influence on obtaining a low self-ignition temperature. The low self-ignition temperature is obtained thanks to the charges which are introduced into the binder.
Selon un premier mode de réalisation de l'invention, la composition comprend un mélange oxydant/réducteur. Un tel mélange oxydant/réducteur doit permettre d'obtenir la bonne température d'autoinflammation. Selon une variante préférée de ce premier mode de réalisation, le liant est un liant époxy, l'oxydant choisi est un chlorate de métal alcalin et le réducteur est un sucre. Dans ce cas, la température d'autoinflammation suffisante est obtenue grâce au couple chlorate de métal alcalin/sucre. Selon une particularité de cette variante, le liant, par exemple une résine époxyde, est présent à un pourcentage massique compris entre 18 et 22% de la masse totale de la composition. Selon une autre particularité, le chlorate de métal alcalin est le chlorate de sodium ou de potassium et il est présent à un pourcentage massique compris entre 30 et 50% de la masse totale de la composition. Selon une autre particularité, le sucre est présent à un pourcentage massique compris entre 15 et 25% de la masse totale de la composition. Selon une autre particularité de cette variante, la composition comprend de l'aluminium et un perchlorate de métal alcalin, pour améliorer la combustion et augmenter le potentiel calorimétrique. Selon une autre particularité, l'aluminium est présent à un pourcentage massique compris entre 5 et 15% de la masse totale de la composition. Selon une autre particularité, le perchlorate de métal alcalin est le perchlorate de potassium, ce composé étant présent dans une proportion inférieure à 20% de la masse totale de la composition.According to a first embodiment of the invention, the composition comprises an oxidizing / reducing mixture. Such an oxidizing / reducing mixture must make it possible to obtain the correct self-ignition temperature. According to a preferred variant of this first embodiment, the binder is an epoxy binder, the oxidant chosen is an alkali metal chlorate and the reducing agent is a sugar. In this case, the sufficient self-ignition temperature is obtained thanks to the alkali metal chlorate / sugar couple. According to a feature of this variant, the binder, for example an epoxy resin, is present at a mass percentage of between 18 and 22% of the total mass of the composition. According to another particular feature, the alkali metal chlorate is sodium or potassium chlorate and it is present at a mass percentage of between 30 and 50% of the total mass of the composition. According to another particularity, the sugar is present at a mass percentage of between 15 and 25% of the total mass of the composition. According to another particular feature of this variant, the composition comprises aluminum and an alkali metal perchlorate, to improve combustion and increase the calorimetric potential. According to another particularity, the aluminum is present at a mass percentage of between 5 and 15% of the total mass of the composition. According to another particular feature, the alkali metal perchlorate is potassium perchlorate, this compound being present in a proportion of less than 20% of the total mass of the composition.
Selon un second mode de réalisation, la composition comprend un composé oxydant et un catalyseur de décomposition de ce composé oxydant. Selon une particularité de ce second mode de réalisation, le liant est une résine époxyde, l'oxydant du perchlorate d'ammonium et le catalyseur de décomposition un composé ferrocénique. Selon une autre particularité, la résine époxyde est présente à un pourcentage massique compris entre 15 et 30%, avantageusement entre 16 et 25%, de la masse totale de la composition. Selon une autre particularité, le perchlorate d'ammonium est présent à un pourcentage massique compris entre 60 à 88%, avantageusement entre 68 et 88%, de la masse totale de la composition.According to a second embodiment, the composition comprises an oxidizing compound and a catalyst for the decomposition of this oxidizing compound. According to a feature of this second embodiment, the binder is an epoxy resin, the oxidizer of ammonium perchlorate and the decomposition catalyst a ferrocene compound. According to another particular feature, the epoxy resin is present at a mass percentage of between 15 and 30%, advantageously between 16 and 25%, of the total mass of the composition. According to another particular feature, the ammonium perchlorate is present at a mass percentage of between 60 to 88%, advantageously between 68 and 88%, of the total mass of the composition.
Un autre but de l'invention est de proposer un générateur de gaz dans lequel un composé jouant le rôle de fusible thermique peut être facilement intégré dans une zone particulièrement exposée thermiquement. Ce but est atteint par un générateur pyrotechnique de gaz comprenant une charge pyrotechnique principale génératrice de gaz permettant par exemple de gonfler un coussin de protection, ce générateur étant caractérisé en ce qu'il comporte un composé pyrotechnique auto-inflammable ayant une composition telle que définie dans l'un des modes de réalisation ci-dessus, et dont la température d'autoinflammation est inférieure à celle de la charge pyrotechnique principale. L'invention est plus particulièrement illustrée dans les exemples suivants :Another object of the invention is to provide a gas generator in which a compound acting as a thermal fuse can be easily integrated in a particularly thermally exposed area. This object is achieved by a pyrotechnic gas generator comprising a main pyrotechnic charge generating gas making it possible, for example, to inflate a protective cushion, this generator being characterized in that it comprises a self-igniting pyrotechnic compound having a composition as defined in one of the embodiments above, and the self-ignition temperature of which is lower than that of the main pyrotechnic charge. The invention is more particularly illustrated in the following examples:
Exemple n°lExample # 1
Le mélange de diverses granulométries de perchlorate d'ammonium ainsi que le taux de liant permet l'adaptation de la rhéologie de la pâte obtenue lors du mélange des matières premières aux besoins de dépose et de conservation du produit pendant la durée de mise en oeuvre. Les caractéristiques principales moyennes en tant que fusible thermique des formulations suivant l'exemple 1 sont les suivantes : - Température d'autoinflammation par chauffage progressif à une vitesse de 5°C/min. comprises entre 180 et 190°C. - Pic de décomposition en DSC à 5°C/min, onset du pic vers 180°C. - Stabilité thermique acquise lors de test de stabilité sous vide à 110°C. - Fonctionnement conservé après passage 400 h à 107°C. Dans l'exemple n°l, la température d'autoinflammation est obtenue par abaissement de la température de décomposition du perchlorate d'ammonium à l'aide de catalyseurs de décomposition. Le liant époxy fait office de réducteur lors de la combustion.The mixture of various particle sizes of ammonium perchlorate as well as the level of binder allows the rheology of the paste obtained during the mixing of the raw materials to be adapted to the requirements for depositing and preserving the product during the implementation period. The main average characteristics as thermal fuse of the formulations according to Example 1 are as follows: - Auto-ignition temperature by progressive heating at a speed of 5 ° C / min. between 180 and 190 ° C. - DSC decomposition peak at 5 ° C / min, peak onset around 180 ° C. - Thermal stability acquired during vacuum stability test at 110 ° C. - Operation retained after passage 400 h at 107 ° C. In Example No. 1, the self-ignition temperature is obtained by lowering the decomposition temperature of ammonium perchlorate using decomposition catalysts. The epoxy binder acts as a reducing agent during combustion.
Exemple n°2Example 2
Les caractéristiques moyennes en tant que fusible thermique des formulations suivant l'exemple 2 sont les suivantes : -Température d'autoinflammation par chauffage progressif à une vitesse de 5°C/min. comprises entre 178 et 185°C. - Pic de décomposition en DSC à 5°C/min, onset du pic vers 180°C. - Stabilité thermique acquise lors de test de stabilité sous vide à 110°C. - Fonctionnement conservé après passage 400 h à 107°C.The average characteristics as thermal fuse of the formulations according to Example 2 are the following: Self-ignition temperature by progressive heating at a speed of 5 ° C / min. between 178 and 185 ° C. - DSC decomposition peak at 5 ° C / min, peak onset around 180 ° C. - Thermal stability acquired during vacuum stability test at 110 ° C. - Operation retained after passage 400 h at 107 ° C.
Dans l'exemple 2, la température d'autoinflammation est obtenue à l'aide du couple chlorate/sucre qui en l'absence de liant permet d'obtenir une autoinflammation vers 160°C. Le chlorate de sodium peut être remplacé par le chlorate de potassium. L'enrobage du chlorate dans un liant permet d'obtenir un produit compatible avec les oxydants à base d'ions ammonium (comme par exemple le perchlorate d'ammonium).In Example 2, the autoinflammation temperature is obtained using the chlorate / sugar couple which, in the absence of a binder, allows autoinflammation to be obtained around 160 ° C. Sodium chlorate can be replaced by potassium chlorate. Coating the chlorate in a binder makes it possible to obtain a product compatible with oxidants based on ammonium ions (such as, for example, ammonium perchlorate).
Le test DSC (pour "Differential Scanning Calorimetry") utilisé dans les exemples 1 à 2 ci-dessus est une méthode d'analyse thermique qui permet de mesurer la puissance thermique libérée ou absorbée par un produit en fonction d'un programme de montée en température (dans les exemples 1 à 2, montée de 5°C par minute). Cette méthode permet de mesurer par exemple des chaleurs spécifiques, des enthalpies reactionnelles ou des énergies de changement de phase. The DSC test (for "Differential Scanning Calorimetry") used in examples 1 to 2 above is a thermal analysis method which makes it possible to measure the thermal power released or absorbed by a product as a function of a rise program. temperature (within examples 1 to 2, rise of 5 ° C per minute). This method makes it possible to measure, for example, specific heats, reaction enthalpies or phase change energies.

Claims

Revendications claims
1. Composition d'un composé pyrotechnique convenant comme fusible thermique dans un générateur de gaz comprenant une charge pyrotechnique, ledit composé pyrotechnique ayant une température d'autoinflammation inférieure à celle de la charge pyrotechnique du générateur de manière à pouvoir initier en combustion la charge pyrotechnique, en cas d'échauffement anormal du générateur, avant que ladite charge pyrotechnique n'atteigne sa température d'autoinflammation, ladite composition étant caractérisée en ce qu'elle comporte un liant, ledit liant étant choisi dans la famille des époxydes ou dans celle des polybutadienes, ledit liant étant présent dans la composition à un taux déterminé de sorte que ladite composition puisse être dosée et déposée sous la forme d'une colle sur tout support approprié du générateur.1. Composition of a pyrotechnic compound suitable as a thermal fuse in a gas generator comprising a pyrotechnic charge, said pyrotechnic compound having a self-ignition temperature lower than that of the pyrotechnic charge of the generator so as to be able to initiate the combustion of the pyrotechnic charge , in the event of abnormal heating of the generator, before said pyrotechnic charge reaches its self-ignition temperature, said composition being characterized in that it comprises a binder, said binder being chosen from the family of epoxides or that of polybutadienes, said binder being present in the composition at a determined rate so that said composition can be dosed and deposited in the form of an adhesive on any suitable support of the generator.
2. Composition selon la revendication 1, caractérisée en ce que le liant est présent dans une proportion supérieure à 15% de la masse totale de la composition, et avantageusement inférieure à 30% de la masse totale de la composition.2. Composition according to claim 1, characterized in that the binder is present in a proportion greater than 15% of the total mass of the composition, and advantageously less than 30% of the total mass of the composition.
3. Composition selon la revendication 1 ou 2, caractérisée en ce qu'elle comprend un mélange oxydant/réducteur.3. Composition according to claim 1 or 2, characterized in that it comprises an oxidizing / reducing mixture.
4. Composition selon la revendication 3, caractérisée en ce que le liant est de type époxy, en ce que l'oxydant est un chlorate de métal alcalin et en ce que le réducteur est un sucre.4. Composition according to claim 3, characterized in that the binder is of epoxy type, in that the oxidant is an alkali metal chlorate and in that the reducing agent is a sugar.
5. Composition selon la revendication 4, caractérisée en ce que le liant de type époxy est présent à un pourcentage massique compris entre 18 et 22% de la masse totale de la composition.5. Composition according to Claim 4, characterized in that the epoxy type binder is present at a mass percentage of between 18 and 22% of the total mass of the composition.
6. Composition selon la revendication 4 ou 5, caractérisée en ce que le chlorate de métal alcalin est le chlorate de sodium ou de potassium et en ce qu'il est présent à un pourcentage massique compris entre 30 et 50% de la masse totale de la composition. 6. Composition according to claim 4 or 5, characterized in that the alkali metal chlorate is sodium or potassium chlorate and in that it is present at a mass percentage between 30 and 50% of the total mass of the composition.
7. Composition selon l'une des revendications 4 à 6, caractérisée en ce que le sucre est présent à un pourcentage massique compris entre 15 et 25% de la masse totale de la composition7. Composition according to one of claims 4 to 6, characterized in that the sugar is present at a mass percentage of between 15 and 25% of the total mass of the composition
8. Composition selon l'une des revendications 4 à 7, caractérisée en ce qu'elle comprend de l'aluminium et un perchlorate de métal alcalin.8. Composition according to one of claims 4 to 7, characterized in that it comprises aluminum and an alkali metal perchlorate.
9. Composition selon la revendication 8, caractérisée en ce que l'aluminium est présent à un pourcentage massique compris entre 5 et9. Composition according to claim 8, characterized in that the aluminum is present at a mass percentage of between 5 and
15% de la masse totale de la composition.15% of the total mass of the composition.
10. Composition selon la revendication 8 ou 9, caractérisée en ce que le perchlorate de métal alcalin est le perchlorate de potassium et en ce qu'il est présent dans une proportion inférieure à 20% de la masse totale de la composition.10. Composition according to claim 8 or 9, characterized in that the alkali metal perchlorate is potassium perchlorate and in that it is present in a proportion of less than 20% of the total mass of the composition.
11. Composition selon la revendication 1 ou 2, caractérisée en ce qu'elle comprend un composé oxydant et un catalyseur de décomposition de ce composé oxydant.11. Composition according to claim 1 or 2, characterized in that it comprises an oxidizing compound and a catalyst for decomposition of this oxidizing compound.
12. Composition selon la revendication 11, caractérisée en ce que le liant est de type époxy, l'oxydant du perchlorate d'ammonium et le catalyseur de décomposition un composé ferrocénique.12. Composition according to claim 11, characterized in that the binder is of the epoxy type, the oxidant of ammonium perchlorate and the decomposition catalyst a ferrocene compound.
13. Composition selon la revendication 12, caractérisée en ce que le liant est présent à un pourcentage massique compris entre 15 et 30% de la masse totale de la composition.13. Composition according to claim 12, characterized in that the binder is present at a mass percentage of between 15 and 30% of the total mass of the composition.
14. Composition selon la revendication 12 ou 13, caractérisée en ce que le perchlorate d'ammonium est présent à un pourcentage massique compris entre 60 et 88% de la masse totale de la composition.14. Composition according to claim 12 or 13, characterized in that the ammonium perchlorate is present at a mass percentage of between 60 and 88% of the total mass of the composition.
15. Générateur pyrotechnique de gaz comprenant une charge pyrotechnique génératrice de gaz, caractérisé en ce qu'il comporte un composé pyrotechnique auto-inflammable ayant une composition selon l'une des revendications 1 à 14 et dont la température d'autoinflammation est inférieure à celle de ladite charge pyrotechnique génératrice de gaz. 15. Pyrotechnic gas generator comprising a pyrotechnic gas generating charge, characterized in that it comprises a Self-igniting pyrotechnic compound having a composition according to one of claims 1 to 14 and whose self-ignition temperature is lower than that of said gas-generating pyrotechnic charge.
EP05770900.8A 2004-05-13 2005-05-11 Dosable pyrotechnic composition usable in the form of a thermal fuse for a gas generator and a gas generator comprising a compound containing said composition Not-in-force EP1748972B1 (en)

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PCT/FR2005/001175 WO2005115948A2 (en) 2004-05-13 2005-05-11 Dosable pyrotechnic composition usable in the form of a thermal fuse for a gas generator and a gas generator comprising a compound containing said composition

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US8029630B2 (en) 2011-10-04
FR2870234A1 (en) 2005-11-18
FR2870234B1 (en) 2007-02-09
JP2007537123A (en) 2007-12-20
CA2565868A1 (en) 2005-12-08
US20070227635A1 (en) 2007-10-04
CA2565868C (en) 2013-07-16
CN1953950A (en) 2007-04-25
CN1953950B (en) 2010-06-16
WO2005115948A2 (en) 2005-12-08
EP1748972B1 (en) 2018-10-17
WO2005115948A3 (en) 2006-05-04
JP4948396B2 (en) 2012-06-06

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